Method of preparing halogenated olefinic derivatives of saturated gamma-keto mono-carboxy acids and related compounds

ABSTRACT

Direct halogenation of C4-C10 saturated keto monocarboxy acids or their acidogenic derivatives with elemental halogen to yield olefinic halogenated compounds (e.g., acids and lactones) containing at least four halogen atoms per molecule is disclosed. The halogenation is purely thermal with preferred temperature ranges being selected as a function of the particular end product desired. Halogenated products of the process as well as ammonia and amine salts of the acids made by the process are useful as insecticides, plant grown control agents and defoliants. Particularly useful products are those olefinic polychlorinated derivatives of gamma-keto-pentanoic acid which contain at least four chlorine atoms per molecule such as, for example, 2,3,5,5,5pentachloro-4-keto pentenoic acid, its ammonium salt and its amine salts.

United States Patent [191 Erby et al.

[111 3,862,220 [451 Jan. 21, 1975 [75] Inventors: William A. Erby, Alburtis; Robert A. Walde, Emmaus, both of Pa.

[73] Assignee: Air Products and Chemicals, Inc.,

Allentown, Pa.

[22] Filed: Aug. 30, 1972 21 Appl. No.: 284,815

Related US. Application Data [60] Continuation of Ser. No. 714,761, March 21, 1968, abandoned, which is a division of Ser. No. 541,096, April 8, 1966, Pat. No. 3,577,546.

[52] US. Cl. 260/539 R, 71/70, 7l/l06, 71/113, 260/343.6, 260/408, 260/479 R,

260/486 D, 260/486 H, 260/501.l5, 260/544 Y, 424/312, 424/314, 424/315, 424/317, 424/318 [51] Int. Cl. C07c 65/00 [58] Field of Search 260/539 R, 343.6

[56] References Cited UNITED STATES PATENTS 2,446,849 8/1948 Price 260/406 2,557,779 6/1951 Britton et al 260/539 2,985,684 5/1961 Pennino 260/479 3,275,505 9/1966 Herschler 260/539 Primary Examiner-.lames A. Patten Attorney, Agent, or Firm-Leroy Whitaker; Everet F. Smith [57] ABSTRACT Direct halogenation of C -C saturated keto monocarboxy acids or their acidogenic derivatives with elemental halogen to yield olefinic halogenated compounds (e.g., acids and lactones) containing at least four halogen atoms per molecule is disclosed. The halogenation is purely thennal with preferred temperature ranges being selected as a function of the particular end product desired. l-Ialogenated products of the process as well as ammonia and amine salts of the acids made by the process are useful as insecticides, plant grown control agents and defoliants. Particularly useful products are those olefinic polychlorinated derivatives of gamma-keto-pentanoic acid which contain at least four chlorine atoms per molecule such as, for example, 2,3,5,5,5-pentachloro-4-keto pentenoic acid, its ammonium salt and its amine salts.

7 Claims, N0 Drawings METHOD OF PREPARING HALOGENATED OLEFINIC DERIVATIVES OF SATURATED GAMMA-KETO MONO-CARBOXY ACIDS AND RELATED COMPOUNDS CROSS REFERENCE TO RELATED APPLICATION This application is a continuation of application Ser. No. 714,761 filed Mar. 21, 1968. now abandoned. which in turn is a division of our prior co-pcnding application Ser. No. 541,096 filed Apr. 8, 1966, now U.S. Pat. No. 3,577,546, entitled Preparation and Use of Polychloro Keto-Alkenoic Acids" which discloses and claims, inter alia, the use of compounds made by the method of the instant invention as pesticides, physiologically active materials and plant growth control agents. It is also related to our prior co-pending application Ser. No. 654,989 filed July 21, 1967 now U.S. Pat. No. 3,619,164, entitled Method of Controlling Growth of Woody Jungle Plants which discloses and claims the use of compositions comprising 2,3,5,5,5-pentachloro-4-keto pentenoic acid, which can be made by the method of the instant invention, for jungle defoliation.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is concerned with novel methods for the synthesis of polyhalogenated and perhalogenated keto alkenoic acids, such as, for example, C to C mono-carboxylic acids, from the corresponding saturated keto acids, their esters, amides, anhydrides, lactones, acyl halides, and other acidogenic derivatives. More particularly, it pertains to methods of directly chlorinating and/or brominating gamma-ketopentanoic acids and their derivatives to obtain acyclic and cyclic olefinic products which contain at least 4 halogen atoms per molecule.

2. Description of the Prior Art While various investigators have reported the chlorination of gamma-keto C to C acids to the mono or dichloro stage, there is no report to date of any direct combined chlorination and dehydrogenation of such acids (or their acidogenic derivatives) to the unsaturated polyhalogenated or perhalogenated stage. As used herein, the terms polyhalogenated and polychlorinated refer, respectively, to compounds containing at least four halogen atoms per molecule (which may be of the same or of different halogens) and to compounds which contain at least four chlorine atoms per molecule. The terms perhalogenated and perchlorinated refer, respectively, to compounds in which all of the hydrogen atoms attached to carbon atoms in the molecule are substituted with halogen atoms (which may be of the same or different halogens), and to compounds in which all of the hydrogen atoms attached to carbon atoms are substituted with chlorine atoms. The term halogen" is intended to include chlorine, bromine or mixtures thereof.

A common gamma-keto-pentanoic acid, which is available in commerce, is levulinic acid. Early attempts to chlorinate levulinic acid directly resulted only in the production of monoand dichloro derivatives. [Seiss], Annallen, 249, 288-303 (1888).] A number of polychloro-pentenoyl ketones. acids, acid halides and anhydrides have since been prepared by methods other than by the direct chlorination of levulinic acid [Zincke, Berichte der Deutsche Chemische Gessellschaft, 23, 240,

LII

(1890); 24, 916, (1891); 25. 2221, (1892); 26, 506, (1893); and 26, 317 (1893)] U.S. Pat. No. 3,275,505 does disclose the direct halogenation of levulinic acid. However, the reaction temperatures are between and C and, even with high degrees of halogenation, no more than four atoms of halogen are added per molecule of levulinic acid. Further, there is no conversion of the acid from a saturated to an olelinic compound.

BRIEF SUMMARY OF THE INVENTION Briefly summarized. the invention pertains to the halogenation, particularly with chlorine, of saturated keto mono carboxylic acids of which levulinic acid is a prime example. It also relates to subsequent esterification and salt formation. While the invention may be utilized in connection with either chlorine or bromine or both, those compounds produced from chlorine and- /or bromine and levulinic acid are possessed of particular utility in connection with growth control of plants and in insecticidal applications. One particular compound, which can be made by processes of the invention, and which is designated as 2,3,5,5,5-pentachloro- 4-keto pentenoic acid has a unique capacity for wilting the foliage of woody jungle plants such as cotton. This characteristic is the basis for a novel method of harvesting cotton which is described in U.S. Pat. No. 3,472,004 entitled Method of Harvesting Cotton of which we are among the inventors. Further, chlorinated compounds of the invention are of value as jungle defoliants. Other uses of the compounds made by the instant process are described in the parent application referred to above.

In most general terms, the invention contemplates the direct chlorination and/or bromination of saturated keto mono carboxylic acids or their acidogenic derivatives (e.g., esters, amides, etc.) over relatively long periods of time and at elevated temperatures. Since the reactions are exothermic, it is usually preferred to halogenate at rates which prevent violent fluctuations of temperature such as would cause product degradation or undue increase in by-product formation. When batch processes are used, it is preferred to raise reaction temperatures gradually as the reaction proceeds over a period of time to the optimum limits.

Conditions utilized are always severe enough to cause both dehydrogenation and the addition of at least four halogen atoms per molecule of acid. Under more severe conditions, additional halogen may be incorporated to reach the perhalogenated state, and further, to cause formation of cyclic compounds.

The reactions can best be illustrated with respect to the chlorination of levulinic acid and the summary discussion which follows is generally related to the exam ples in the discussion of the preferred embodiments below. These embodiments utilize levulinic acid or acidogenic derivatives thereof.

In the instant process, the acid or acidogenic material is reacted with gaseous chlorine while the temperature is gradually increased from ambient to a maximum final temperature of 270C. Where the starting material is levulinic acid and the reaction is terminated at to C, the final product will be preponderantly a tetra-ch10ro-4-keto-pentenoic acid. Where the reaction is terminated between 190 and 210C the reaction product is a pentachloro-4-keto pentenoic acid. Where the reaction is terminated at a final temperature of 2 1 2 to 260C, the final product is a hexachloro-Z-pentenoic acid-4-lactone. It has been found that, where it is desired to produce an end product which is substantially pure 2,3,5,5,5,-pentachloro-4-keto-pentenoic acid, the most effective technique for obtaining a pure product is to terminate the reaction at temperatures above 212C, to produce the corresponding lactone and to, thereafter, utilize acid hydrolysis, preferably in the presence of chlorine gas, to convert the lactone to the desired acid. Reaction times are on the order of 90 hours.

The above reactions may be conducted with bromine instead of chlorine. Further, a reaction may be begun with one type of halogen, discontinued before perhalogenation is completed, and reacted with yet another halogen to the completion of halogenation so that a given molecule will contain atoms of different halo- The halogenated compounds produced by the novel method of the present invention from 5 carbon keto carboxy acids correspond, in form of the carboxylic acids or their esters, to the formula.

C, O Cl H, COOR thereof) are:

253, l,5, 5, S-hexaehloro-Q-pentenoyl-U- laetone (perehloro angelica lactone) 0 c1 c1 0 2) 1 it I ii 0 c H c c c c 3 5. pheny1-2 3,5,5,5-pentachlorol-ketc-2- pentenoate H o j 01 c1 0 3) 1 ill A ll c1 0 c c c 0H 1 2,3,5,5-te%raehl0r0 -l-keto-2-pentenoic acid 0 '01 H o 4 II I I II 01 0 c c c c 0H 3,5,5,5-tetraehlorol-keto-2-pentenoic acid 0 1 o 5) c1 c c c ll o c H 2 5 ethyl 2,5,5,S-tetraehloro-h-keto-2-pentenoate c1 0 c err d c 0' may ammonium salt of 2,5,5, 5-tetrachlorolketo-Q-pentenoia acid wherein R, is alkyl and R and R are each alkyl or hydrogen, these compounds being amine salts of 2,3,5,5,- S-pentachloro-4-keto-2-pentenoic acid The polychloro-compounds so produced have been found to have pronounced activity as insecticides, herbicides and cotton defoliants, such that, in a process based upon low cost levulinic acid and chlorine, commercially valuable biologically active chemicals can be produced at low cost.

Esterification of the free acid can be effected with monohydric or polyhydric alcohol. Thus. by reacting compound l with pentaerythritol, a mixture comprising monoand di-esters may be obtained.

Ammonium and amine salts of the free acids can also be formed by reacting the same, respectively, with ammonia or primary, secondary or tertiary alkyl amines including, for example, dipropyl amine, isopropyl amine, N,N-dimethyl hexadecylamine, N-N-dimethyl octadecylamine, N-Ndimethyl dodecylamine and cocoamine.

Accordingly, it is an object of the invention to provide a method whereby direct halogenation of C, to C saturated keto mono carboxy acids or their acidogenic derivatives at changing temperatures may be utilized to effect both halogenation and dehydrogenation.

It is a further object of the invention to provide a direct method of halogenation where, selectively, dependent upon the reaction conditions utilized and the reactants present, one may obtain acyclic halogenated olefinic keto acids or related cyclic compounds both of which are capable of further reactions such as esterification.

lt is additionally an object of the invention to provide processes for the direct thermal chlorination of keto carboxy acids.

These and other objects of the invention will be apparent to those skilled in the art from a consideration of the exemplary description which follows.

It should be appreciated that neither the abstract of the disclosure nor the summary of the invention above is intended to constitute a limitation on its extent. They are inserted merely as aids in information retrieval and, therefore, the true scope of the invention is to be determined only by a reasonable interpretation of the appended claims in light of the disclosure herein contained.

DESCRIPTION OF PREFERRED EMBODIMENTS The desired compounds are produced, in accordance with the invention, for example, by passing chlorine into levulinic acid or into an acidogenic derivative of levulinic acid over an extended period of time while raising the temperature gradually from ambient temperature to an ultimate temperature in the region of 150 to 270C. As halogen is added, the activation energy for subsequent substitutions increases. Therefore, it is necessary to increase the temperature as the reaction proceeds although, in equivalent continuous processes, cold feed can be added to large agitated bodies of liquid maintained at optimum temperature and such rt s=s1. s 2ftn tadssllyts n temperature Premature elevation of temperature can induce decomposition and polymerization of unsuitable intermediates. However, the thermal stability of the intermediates increases as the halogen content increases, which allows the reaction temperature to be safely increased as halogenation proceeds. Since the reactions are exothermic, once they have been initiated, it is important to control the rate of addition of halogen so that tematoms per molecule. The acids obtained can be readily converted to the correspondingsalts, esters and amides by methods generally known in the art.

The distinct properties of the compounds obtained by the practice of the invention which render them useful, and effective as insecticidal and herbicidal compositions, are believed to reside in the simultaneous presence in the carboxylic compound of the polychloro function combined with the effect of the olefinic linkage, and the keto type structure. Despite the high insecticidal activity displayed by these compounds, they are highly selective in their action on plants, whereby they also have utility as plant growth control and defoliating agents.

The following examples illustrate the purely thermal embodiments of the invention but are not intended to limit the same.

EXAMPLE 1 Chlorine gas was passed continuously through 588 g. of ethyl levulinate with rapid mixing. The temperature rose exothermally to 60C and remained there for 26 hours. When the temperature started to fall, heat was applied to raise the temperature to l l2C. The temperature of the reaction was then allowed to rise slowly, with further chlorination, to I80C, and kept there for 35 hours. More heat was applied and the temperature was further increased to 2] 2C and held at that temperature for 14 hours. The total reaction time thus was hours. At the end of this period, the chlorine content of the product was 70.5 percent and 1,435 grams of material were recovered. Gas chromatographic, infrared spectrographic, ultimate analysis and other physical tests showed 93 percent of the product to consist of the 2,3,4,5,5,S-hexa-chloro-2-pentenoyl-4-lactone,

(i.e., perchloro-angelica lactone) having the following t formula: W A

Boiling Point 74,5C/(l.2 mm Hg Refractive Index, 20ID 1.5465 Density, g/ml at 20C 1.6357

Found Theory Chlorine Content 70.271 69.8% Carbon Content 20.2% 19.8% Molecular Weight 3 I5 305 Strong characterizing adsorption peaks for infra-red were at 1835 cm and 974 cm. Weight recovery on the basis of this structure was 94 percent of theoretical.

Halogenated angelica lactone behaves, in various chemical reactions, as if it were an acyl halide of the type:

Thus, it esterified by reaction with sodium phenoxide to yield a phenyl ester of pentachloro-4- keto-Z-pentenoic acid.

EXAMPLE 2 1 1.6 lb. of levulinic acid were placed in a vessel with a sintered glass sparger which allowed rapid and unifrom which the structural formula was indicated to be:

e1 -c=c-c-oa 2,3, 5,5,5-pentachloro-4-keto-2-pentenoic acid form dispersion of elemental halogen through the contents. Chlorine was passed rapidly into this system, with the initial temperature maintained below 90C by external cooling. After 24 hours of chlorination, hydrogen chloride evolution decreased noticeably. The temperature was then raised to 125C for 24 hours while an excess of chlorine was maintained in the reaction system (as evidenced by the presence of free chlorine in the reactor exit gas and yellow color in the reactor solution). The temperature was then slowly increased to 170C and maintained at that temperature for over '8 hours, with continuous chlorine additional until HCl evolution again diminished. The reaction product crystallized on cooling.

A sample of this product, after recrystallization, was a white solid having a melting point of ll7l18C. While the reaction product might have been expected to be a broad mixture of trichloro to hexachlorocompounds with numerous stereo-isomers, the product was, surprisingly, predominantly the unsaturated tetrachloro-keto acid with very little trichloro or pentachloro acid present.

EXAMPLE 3 Using essentially the same equipment as in Example 2, levulinic acid was chlorinated directly by the introduction of chlorine. The initial reaction temperature held at 60 to 90C until about one-third of the total chlorine had been introduced and reacted. After the initial one-third had reacted, the reaction temperature was allowed to increase slowly, by the exothermic heat of chlorination, to the vicinity of 170C and, by supplementary heating, to 190 to 200C while maintaining a substantial excess of chlorine. The reaction mixture was held in the temperature range of 190 to 200C until there was a substantial drop in the rate ofchlorine absorption and HCl release. At this point, a sample withdrawn from the reactor and washed with n-heptane gave a white crystalline product found, on ultimate analysis, to be principally C Cl,-,HO Analytical results were as follows:

Infra-red analysis showed the following characteristic peaks:

EXAMPLE 3-A Cis-configuration of this structure was confirmed by production of the same unsaturated polychlorocompound by the acid hydrolysis of the related hexachloro-angelica-lactone of Example 1.

EXAMPLE 4 To further point up the criticality of temperature in direct chlorination by the present process, the reaction product of Example 3, principally the pentachloro-4- keto-pentenoic acid, was then heated from 200C to about 260C with the continuous addition of chlorine. After 24 hours, at 250 to 260C, the reaction product was practically completely converted to the liquid unsaturated hexachloro-lactone of Example 1.

EXAMPLE 5 Levulinic acid (11.6 lbs.) was placed in a reactor equipped with a gas dispersion tube, a stirrer and a heating-cooling mechanism. Chlorine (26 lbs/hr) was then passed through the dispersion tube into the rapidly stirred mixture. An exothermic reaction occurred, and the temperature was allowed to increase to C. It was maintained at this temperature by proper adjustment of the cooling bath. The reaction was allowed to continue until a decrease in the reaction exotherm was indicated by a drop in the temperature inside the reac- 101'.

On completion of this phase of the reaction, the temperature was slowly raised to l30-140C by increasing the temperature of the bath. Care was taken during this operation to prevent darkening of the reaction mixture caused by raising the temperature too rapidly. Again an exotherm was noted. The chlorine flow rate during the rest of the reaction was maintained fast enough to insure that a small amount of chlorine was in the reactor exit gas. The reactor was held at this temperature until the heat output of the reaction again decreased.

Upon completion of the second phase, the temperature was again raised to 250C. The reaction was then maintained at this temperature until completion of the reaction. This was confirmed by infra-red analysis of the sample. The spectrum contained no absorption peak between 2.5 and 3.5 microns. A very sharp carbonyl absorption band of high intensity appeared at 5.45 microns. This was accompanied by a small shoulder at 5.55 microns. An unsaturation absorption band was also evident at 6.15 microns.

The reaction product was thus shown to be predominantly 2,3,4,5,5,5,hexachloro-2-pentenoyl-4-lactone.

The reaction product of Example 5 was converted quantitatively to 2,3,5,5,5-pentachloro-4-keto pentenoic acid using the following hydrolysis technique.

The reaction product was adjusted in temperature to lC and 3.48 lbs. of water added (i.e. 30 percent of the levulinic acid charge). The reaction mixture was then rapidly stirred while a slow stream of chlorine was passed through the system while the temperature was maintained at l()0C.

When this hydrolysis was complete, the carbonyl region of the infra-red spectrum of the product showed two bands, one at 5.5 and one at 5.6 microns. A broad acid-OH absorption band appeared at 3 microns. The

temperature was then allowed to drop to approximately 90. Water was added until phase separation occurred. The water in the upper layer was then siphoned out as completely as possible. The product was washed two more times with water and dried.

The total yield of product under these conditions, was in the neighborhood of 80 percent. The remainder ofthe material was presumed lost by entrainment in the exit gases at the high temperature, or by break-down to dichloromaleic anhydride. The dichloromaleic anhydride formation could account for about 10 percent of the lost product.

chlorination according to the invention are fully olefinically unsaturated at the tetra-. pentaand hexachloro levels. Unless temperature is carefully controlled, particularly during the early stage ofhalogenation, one obtains only polymeric products of a tarry nature.

The process of producing unsaturated polychloro-4- keto-pentenoic acid or its acidogenic derivatives, with at least four chlorine atoms per molecule, has been exemplified above starting with levulinic acid or its ester. However, the process is not limited to these starting materials alone. Acyl halides, anhydrides and lactones of levulinic acid can be used, and, since chlorination of levulinic acid and its acidogenic derivatives to monochloroand dichloro-state has been effected heretofore, such intermediately chlorinated derivatives can be used as well, whether chlorine is in the alkyl chain, in the acyl group, or in both. Homologous keto acids and keto acids relatable to levulinic acid which contain the structure:

0 H H O I ll rC-CC-C i l R1R2 wherein R, and R are independently selected from the group consisting of hydrogen, halogen and lower alkyl are similarly polychlorinatable or perchlorinatable according to the invention.

Directchlorination of levulinic acid readily forms the While the invention is principally concerned with simple chloro-derivative. The reaction has been shown chlorination, it will be understood that other halogenaby others to proceed with increasing difficulty only to tion'reactions, such as bromination, can also be efthe tetrachloro stage. Surprisingly, we have found that fected by stepwise temperature elevation during haloon extended chlorination at 170 to 270C. preferably genation to obtain corresponding unsaturated keto below 250C, in the presence of an excess of chlorine, acids having four or more bromine substituents. that four or more hydrogen atoms are substituted by Other examples of similar reactions utilizing chlochlorine atoms and two hydrogen atoms are simultarine, bromine or both are presented below in tabular neously split off (as HCl) to produce a new species of form. The techniques utilized were generally similar to olefinically unsaturated derivatives. The products of those described in Example 5.

Example Max. Total No. Starting Acid Halogen Tern. Time Product 7 Levulinic Br C 16 2.3.5.5.tetrabromo-4-ketopentenoic acid 8 Levulinic Bl'g 200C 16 2.3.5,5,5-pentabromo-4-ketopentenoic acid 9 Levulinic Br 250C 80 2,3.4.5.5,5hexabromo-2- pentenoyl-4-lactone l0 Levulinic Br then 200C 16 2.5.5-trichloro-3,5-dibrorno- C 2 4-ketopentenoie acid It 4-keto-hexanoic acid Cl. 220C 30 2.3.4.5.5.6.6-heptuchloro hexenoyl-4-lactone l2 5-methyl-4-oxo-hexanoic Cl, 215C 30 2.3.4,5.6.6-hexachloro-5- acid trichloromethyl-4-hexenonyl lactone l3 6-hydroxy-6,6-di- Cl; C 40 2.3.5.5.h-hexachloro-6,( -ditrifluoromethyl-l-keto trifluoromethyl-4-keto-hexenoic acid hexanoic acid 14 6,6-dimethyl-4-keto Cl 200C 30 2,3.4.5.5.-pentachloro-6.6-

heptanoic acid dimethyl-4-heptanoyl lactone l5 5,5,6-trimcthyl C12 225C 35 2.3.4.5 tetrachloro 5,6,6-

-4-keto heptanuic acid trimethylA-heptanonyl lactone l6 4-ketohexanoic acid Br 230C 40 2.3.45.5,6.6.6-octahromo hexanoyl-4-lactone l7 6,6-dimethyl-4 keto Br, 230C 40 2.3.4.5.5.6-hexabromo-h.h-

heptanoie acid dimethyl heptanoyl-4-lactone Definite temperature limits have been shown for each halogenation step. However, it will be appreciated by those conversant with the art that reasonable variations can be made in the prescribed temperature and time of halogenation by which the rate and extent of halogenation and dehyrogenation can be varied in any step of the process. For instance. whereas chlorination and dehydrogenation of ethyl levulinate was affected over periods as long as 72 hours with rising temperature and'with a significant quotient of reaction time at or above 2l0C., a similar degree of chlorination and dehydrogenation might be effected in somewhat shorter time, though with probably less selectivity, at moderately higher temperatures.

After the reactions described above, the reaction products may be further reacted to produce esters, am-

ides and salts. When salts are desired of those products which are lactones, it is first necessary to obtain the free acid form by hydrolysis. The following are illustrative examples of salt formation:

EXAMPLE S-l a linear numerical scale where indicates no effect and indicates a complete kill I we; Pigweed l0 Johnsongrass 9 Setaria 8 B. Crops Corn 6 Oats 2 Wheat 1 Another utility possessed by compounds which can be made using the processes of the instant invention arises in connection with the wilt-harvesting of cotton. Application of these materials to cotton prior to harvesting causes wilting offoliage to occur in a short time and promotes boll opening. By harvesting cotton when the plant is wilted yield and quality of cotton are improved. Further, thereafter, defoliation occurs and the balance of the cotton can be harvested. All of these ag- 'ricultural techniques are discussed at length in U.S. Pat. No. 3,472,004 referred to above. Suffice it to say at this point, that it is commercially desirable for the compounds under consideration to wilt and/or defoliate cotton plants. Some test data demonstrative of this ability is given below in a series of tests performed with the compound of Example 3 and various of its salts.

Applications of the indicated compound at the rate of active ingredient shown was in the form of a water extendible concentrate which was diluted to a spray volume equivalent to gallons per acre.

Rate "/r Wilt 7n Defoliation Compound of (lbs/acre) 24 hrs. 48 hrs. 5 days I} days I Example 3 4 80 80 50 50 2 Ammonium salt 4 80 90 95 95 3 Monomethyl amine 4 40 40 4 Monethyl amine salt 4 50 55 3O 30 5 Monoisopropyl amine salt 4 55 7O 20 20 6 Triethylamine salt 4 5 5 7 Monoethanolamine salt 4 40 40 25 2 8 Triethanolamine salt 4 20 2O 2 2 EXAMPLE 5-2 The product of Example 3-A, subsequent to the hydrolysis step, was subjected to the method of Example S-] and the same ammonium salt was obtained as from Example 5-].

Salts of the various halogenated keto acids of the invention are obtained by reacting them (in their acid form) with ammonia or organic amines, preferably those containing from one to 18 carbons. As used henceforth herein, the term organic amines is intended to encompass such compounds as well as amines which have been reacted with an alkylene oxide. Amines which have been utilized in this connection include n-octylamine, N-oleyl-l,3-propylene diamine, ethylamine, diethyl amine, triethylamine, propylamine, dipropyl amine, isopropyl amine, ethanol amine, diisopropyl amine, butyl amine, dibutyl amine, hexyl amine, 2-Ethylhexyl amine, N-methylbutyl amine, etc.

One of the utilities of the compounds of the process is exemplified by data obtained using the product of Example 1 as the active ingredient. Herbicidal characteristics were determined by spraying the active material at a rate of2 lbs/acre using a water suspendable oil formulation thereof. In the table results are reported on 50 out departing from the spirit and scope thereof. Therefore, only such limitations should be imposed as are indicated in the appended claims.

We claim:

1. A method for producing C C polyhalogenated gamma-keto monocarboxy alkenoic acids having at least four halogen atoms per molecule which comprises the direct combined halogenation and dehydrogem ation of C -C gamma-keto-monocarboxy alkanoic acids by treatment with elemental halogen initially at substantially ambient temperature and gradually rais' ing the temperature to a final temperature of between 170 C. and 270 C., the reaction being conducted at a rate sufficient to prevent product degradation and undue by-product formation, said halogen being selected from the group consisting of chlorine, bromine and mixtures thereof.

2. The method of claim 1 wherein the final temperature is between 170 C. and l C 13 3. The method of claim 2 wherein the starting alkanoic acid is levulinic acid, the halogen is chlorine, and the final product contains a preponderance of tetrachloro-{l-ketopentenoic acid.

4. The method ofclaim 1 wherein the final temperature is between 190 C. and 210 C.

5. The method of claim 4 wherein the starting alkamine. 

2. The method of claim 1 wherein the final temperature is between 170* C. and 190* C.
 3. The method of claim 2 wherein the starting alkanoic acid is levulinic acid, the halogen is chlorine, and the final product contains a preponderance of tetrachloro-4-ketopentenoic acid.
 4. The method of claim 1 wherein the final temperature is between 190* C. and 210* C.
 5. The method of claim 4 wherein the starting alkanoic acid is levulinic acid, the halogen is chlorine, and the final product contains a preponderance of 2,3,5,5,5-pentachloro-4-ketopentenoic acid.
 6. The method of claim 1 wherein the halogen is chlorine.
 7. The method of claim 1 wherein the halogen is bromine. 